Photographic processing composition containing bis-triazinylarylenediamine derivative and diaminostilbene derivative, and image-formation process using the same

ABSTRACT

The present invention provides a processing composition for a silver halide color photographic photosensitive material. The processing composition has excellent functions of reducing stain caused by residual dyes in a photosensitive material and of making no segregated deposit even in low temperature storage of the processing composition. The processing composition of the invention contains a bis-triazinylarylenediamine derivative and a diaminostilbene derivative. The invention also provides an image-formation process using the processing composition of the invention.

FIELD OF THE INVENTION

The present invention relates to a processing composition for a silverhalide color photographic photosensitive material. In particular, theinvention relates to a composition having excellent functions ofreducing stain caused by residual dyes in a photosensitive material andof making no segregated deposit in low temperature storage of theprocessing composition.

BACKGROUND OF THE INVENTION

In the drastic progress of digital cameras as well as color printers, ithas been desired that high quality images would rapidly be provided forcustomers in processing of color photographic photosensitive materials.However, when conventional processing processes had been conducted in asimply shortened time, the resulted image became colored to a level ofobjection with a large amount of sensitizing dyes remained in a whitepart of color print. Because of the simply shortened time of processing,sensitizing dyes in a photosensitive material were not enough washed outuntil processing had been completed. Also in case of a color negativefilm, such a situation occurred that production of the proper printsbecame impossible because of deterioration of color balance due todensity increase at the minimum density area.

Further in recent years, tabular grains of silver halide as an importantfundamental technique have been used in a highly photosensitive materialfor taking photographs. This technique gives effects of improvingphotosensitivity and a ratio between photosensitivity and graininess,since an amount of sensitizing dye used in a unit of volume can beincreased. On the other hand, the technique gives an increase of dyeamount remained in the photosensitive material after processing. In someprocessing conditions, the increase of residual amount of sensitizingdye can not be neglected but it results in phenomena that a density atthe minimum density area of color negative film increases and that ahighlight area of color reversal film is stained.

Research Disclosure No. 20733 discloses a method using abis-triazinylaminostilbene disulfonic acid compound as an example of amethod for removing residual colors caused by sensitizing dyes. Thismethod has widely been used in processing of color photographicphotosensitive materials. Japanese Patent Laid-Open No. 329936/1994discloses bis-triazinylaminostilbene disulfonic acid compounds havingexcellent solubility and being able to reduce residual colors even aftertime-shortened processing.

However, further condensation of a processing composition has beendesired due to reasons of reducing waste containers, improving abilityfor recycling and reducing cost of transportation and storage. Anycompound that dissolves in a stable state even under a high saltconcentration by condensation and shows sufficient effects when used atits solubility or less even in a time-shortened processing has not beenfound yet.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a processingcomposition for a silver halide color photographic photosensitivematerial for achieving reduction of stain caused by sensitizing dyesremained in a photosensitive material after processing and for making nosegregated deposit even in low temperature-storage of the processingcomposition.

The problems described in the above were solved by the followinginvention.

1. A processing composition for a silver halide photographicphotosensitive material, comprising a compound represented by Formula(I) described below and a compound represented by Formula (II) describedbelow.

In Formula (I), X₁, X₂, Y₁ and Y₂ each independently represent an alkoxygroup, an aryloxy group, an anilino group, an alkylamino group, adialkylamino group or a nitrogen-containing heterocyclic group, ahydroxyl group, an amino group and a chloro group, which may besubstituted. L represents a substituted or unsubstituted phenylene groupor a substituted or unsubstituted naphthylene group.

In Formula (II), X₃, X₄, Y₃ and Y₄ each independently represent analkoxy group, an aryloxy group, an anilino group, an alkylamino group, adialkylamino group or a heterocyclic group, a hydroxyl group, an aminogroup and a chloro group, which may be substituted. M represents ahydrogen atom, an alkali metal; an alkali-earth metal, ammonium orpyridinium.

2. The processing composition for a silver halide photographicphotosensitive material as described in the foregoing 1 to be used incolor development processing.

3. The processing composition for a silver halide photographicphotosensitive material as described in the foregoing 1 or 2 to be usedin processing of a silver halide color print photosensitive material.

4. An image-forming process using the processing composition for asilver halide photographic photosensitive material as described in anyone of the foregoing 1 to 3.

The compound represented by Formula (I) of the invention gives nofluorescence and the compound represented by Formula (II) hasfluorescent whitening function. By using these compounds together inprocessing of color print materials, it has become possibleindependently to control fluorescent whitening function and reduction ofstain caused by sensitizing dyes. Accordingly, it has become possible toobtain compatibility between fluorescent whitening and reduction ofstain, since stain can be reduced without density lowering in a shadowarea and gradation softening due to excessive use of a fluorescentwhitening agent. Further, by using both of the compound represented byFormula (I) and the compound represented by Formula (II) in combination,it has been found that each solubility of these compounds increases tomake preparation of a more condensed processing composition possible. Ithas also been found that other components in the processing solutionincrease their solubility, and particularly, a developing agentincreases its solubility.

DETAILED DESCRIPTION OF THE INVENTION

Formula (I) will be explained in detail hereinafter. When X₁, X₂, Y₁,and Y₂ each represent an alkoxy group, an aryloxy group, an anilinogroup, an alkylamino group and a dialkylamino group, which may besubstituted, these are expressed by Formula (III) as described below.Formula (III):

—O—R₁  —NHR₂  —NK₂R₃

In Formula (III), R₁, R₂ and R₃ are a substituted or unsubstituted alkylgroup, or a substituted or unsubstituted aryl group. When a grouprepresented by R₁, R₂, or R₃ is an alkyl group, the alkyl group is asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms,preferably 1 to 8, and more preferably 1 to 4. Examples of the alkylgroup include a methyl group, an ethyl group, an i-propyl group, an-propyl group, a n-octyl group, a sulfomethyl group, a 2-hydroxyethylgroup, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-sulfoethylgroup, a 2-methoxyethyl group, a 2-(2-hydroxyethoxy)ethyl group, a2-[2-(2-hydroxyethoxy)ethoxy] ethyl group, a2-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy} ethyl group, a 2,3-dihydroxypropyl group, a 3,4-dihydroxybutyl group and a2,3,4,5,6-pentahydroxyhexyl group.

When R₁, R₂ and R₃ represent an aryl group, the aryl group is asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms,preferably 6 to 10, and more preferably 6 to 8. Examples of the arylgroup include a phenyl group, a naphthyl group, a 3-carboxyphenyl group,a 4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenylgroup, a 2-sulfophenyl group, a 4-sulfophenyl group and a2,4-disulfophenyl group.

When R₁, R₂ and R₃ have a carboxyl group or a sulfo group, these groupsmay be a free body or a salt. In this case, a counter ion is an alkalimetal, an alkali-earth metal, ammonium or pyridinium. Among them, sodiumand potassium are most preferred.

X₁, X₂, Y₁ and Y₂ may be a one-valent (monovalent) 5- or 6-membered ringgroup in which a hydrogen atom bonding to a nitrogen atom is removedfrom a 5- or 6-membered aromatic or non-aromatic nitrogen-containingheterocyclic compound. Examples of the ring include a pyrrolidine ring,a piperidine ring, a piperazine ring and a morpholine ring, which may besubstituted.

Otherwise, X₁, X₂, Y₁ and Y₂ may be an amino acid residue in which ahydrogen atom of an amino group is removed and the amino group forms alinking group, or may be a hydroxy organic acid residue in which ahydrogen atom of a hydroxyl group is removed and the hydroxyl groupforms a linking group.

A phenylene group or a naphthylene group represented by L is asubstituted or unsubstituted phenylene or naphthylene group having 6 to20 carbon atoms, preferably 6 to 15, and more preferably 6 to 11.Examples of the substituted or unsubstituted phenylene or naphthylenegroup include a 1,4-phenylene group, a 1,3-phenylene group, a1,2-phenylene group, a 1,5-naphthylene group, a 1,8-naphthylene group, a4-carboxy-1,2-phenylene group, a 5-carboxy-1,3-phenylene group, a3-sulfo-1,4-phenylene group, a 5-sulfo-1,3-phenylene group, a2,5-dimethoxy-1,4-phenylene group and a 2,6-dichloro-1,4-phenylenegroup.

L is preferably a 1,4-phenylene group, a 1,3-phenylene group, a1,2-phenylene group, a 1,5-naphthylene group and a5-carboxy-1,3-phenylene group, and more preferably a 1,4-phenylene groupand a 1,3-phenylene group.

Specific compounds represented by Formula (I) will be indicatedhereinafer. However, compounds involved in the present invention shouldnot be construed as being limited thereto.

Formula (II) will be explained in detail hereinafter.

When X₃, X₄, Y₃ and Y₄ each represent an alkoxy group, an aryloxy group,an anilino group, an alkylamino group and a dialkylamino group, whichmay be substituted, these are expressed by Formula (IV) as describedbelow. Formula (IV):

—O—R₄  —NHR₅  —NR₅R₆

In Formula (IV), R₄, R₅ and R₆ represent an alkyl group, or an arylgroup. When a group represented by R₄, R₅ or R₆ is an alkyl group, thealkyl group is a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, preferably 1 to 8, and more preferably 1 to 4. Examples ofthe alkyl group include a methyl group, an ethyl group, an i-propylgroup, a n-propyl group, a n-octyl group, a sulfomethyl group, a2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group,a 2-sulfoethyl group, a 2-methoxyethyl group, a 2-(2-hydroxyethoxy)ethylgroup, a 2-[2-(2-hydroxyethoxy)ethoxy] ethyl group, a2-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy} ethyl group, a2,3-dihydroxypropyl group, a 3,4-dihydroxybutyl group and a2,3,4,5,6-pentahydroxyhexyl group.

When R₄, R₅ and R₆ represent an aryl group, the aryl group is asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms,preferably 6 to 10, and more preferably 6 to 8. Examples of the arylgroup include a phenyl group, a naphthyl group, a 3-carboxyphenyl group,a 4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenylgroup, a 2-sulfophenyl group, a 4-sulfophenyl group and a2,4-disulfophenyl group.

X₃, X₄, Y₃ and Y₄ may be a one-valent 5- or 6-membered ring group inwhich a hydrogen atom bonding to a nitrogen atom is removed from a 5- or6-membered aromatic or non-aromatic nitrogen-containing heterocycliccompound. Examples of the ring include a pyrrolidine ring, a piperidinering, a piperazine ring and a morpholine ring, which may be substituted.

Otherwise, X_(3,) X₄, Y₃ and Y₄ may be an amino acid group in which ahydrogen atom of an amino group is removed to make a connection or ahydroxy organic acid group in which a hydrogen atom of a hydroxyl groupis removed to make a connection.

Among alkali metals and alkali-earth metals represented by M, sodium andpotassium are particularly preferable. As an ammonium group, ammonium,triethylammonium and tetrabutylammonium are mentioned.

Specific compounds represented by Formula (IV) will be indicated below.However, compounds involved in the invention are not construed as beinglimited thereto.

In case that a compound represented by Formula (I) and a compoundrepresented by Formula (II) of the invention contain a plurality ofasymmetric carbon atoms in the molecule, there exist a plurality ofstereoisomers for the same structure. The invention involves all thepossible stereoisomers. These stereoisomers can be used as a single kindor some kinds of them in combination.

Compounds represented by Formula (I) and compounds represented byFormula (II) of the invention can be used as a single kind or as pluralkinds in combination. The number of compounds to be used and the sort ofprocessing composition in which these compounds are contained canoptionally be selected.

The processing composition of the invention will be explained in detailhereinafter. In the invention, the processing composition means aprocessing composition necessary for processing to performimage-formation of a silver halide color photographic photosensitivematerial. Specifically, a color development composition, a bleachcomposition, a blix (bleach and fix) composition, a fix composition, awashing composition and a stabilization composition are mentioned as theprocessing composition. Further, a black-and-white developmentcomposition, a reversal composition and a pre-bleach composition may bementioned. Each processing composition described in the above alsoinvolves prepared processing agent compositions to be mixed. Theprocessing composition of the invention is preferably a colordevelopment composition and a black-and-white development composition,and particularly a color development composition. Above all, the effectsof the invention are effectively revealed when the processingcomposition of the invention is applied to a color developmentcomposition for a color print material. These processing compositionsmay be prepared as a tank solution or a replenishing solution in eitherconcentration of a use solution or of a condensed solution. When theprocessing composition of the invention is a condensed solution, it isused as a replenishing solution or as a tank solution after being mixedwith water at a ratio determined for the use. The compounds of theinvention are characterized in that the composition in a solution statehas excellent stability against segregation, therefore, the effects ofthe invention are remarkable in case of a single solution or in case ofprepared processing agent compositions in a condensed solution form tobe mixed. However, the compounds of the invention may be used in each ofprocessing agent compositions in a granular form, a tablet form, apowder form or a slurry form.

Further, the composition of the invention may be an additivecomposition. The additive composition means a composition havingfunctions of controlling photographic properties by adding into a tanksolution or a replenishing solution to be needed for processing toperform image-formation of a silver halide color photographicphotosensitive material.

In the processing composition of the invention, each of concentrationsof the compounds represented by Formula (I) and Formula (II) is in therange from 0.05 mmol/L to 20 mmol/L in the state of a use solution,preferably from 0.15 mmol/L to 15 mmol/L, and more preferably from 0.2mmol/L to 10 mmol/L. The molar ratio of the compound of Formula (I) tothe compound of Formula (II) is generally 1:10 to 10:1, preferably 1:5to 5:1, more preferably 1:3 to 3:1. Besides, in case that the processingcomposition or the invention is used after being diluted with water orwith other processing composition, the concentration of the processingcomposition takes a value made of the concentration of the use solutionmultiplied by the condensation ratio.

The image-formation process of the invention employs the processingcomposition of the invention in at least one of processing processes.The processing composition of the invention may be used in a pluralityof processes or in all the processes.

There are some methods as a manufacture method of the processingcomposition of the invention. The following three methods give goodresults. However, in the execution of the invention, the manufacturemethod should not be construed as being limited to the following threemethods.

[Method A] A method in which a little quantity of water is preliminaryintroduced into a mixing tank, and then chemicals of the composition areadded in order respectively into the tank while being stirred.

[Method B] A method in which chemicals of the composition arepreliminary mixed in a mixing tank, and then a little quantity of wateris added at once into the tank.

[Method C] A method in which chemicals of the composition arepreliminary divided into adequate numbers of groups, each group isdissolved in water or in a hydrophilic organic solvent to be aconcentrated solution, and then concentrated solutions are mixedtogether.

Further, a manufacture method in which each method is partly involvedcan be conducted.

Regarding the case where the processing composition of the invention isa development composition, a bleach composition, a blix composition, afix composition, a washing composition and a stabilizing composition oran additive composition, each composition will be explained hereinafter.

The color development composition of the invention contains a colordeveloping agent. For the color developing agent, known aromatic primaryamine color developing agents are preferable, and particularlyp-phenylenediamine derivatives are preferable. Typical examples will beindicated hereinafter. However, the invention should not be construed asbeing limited thereto. Further these years, among black-and whitephotosensitive materials, there are some materials in which couplers areadded to develop black color for forming a black-and-white image even byusing a color developing solution for general use. The processingcomposition of the invention can be applied to such a kind ofphotosensitive material.

1) N, N-diethyl-p-phenylenediamine

2) 4-amino-N, N-diethyl-3-methylaniline

3) 4-amino-N-(β-hydroxyethyl)-N-methylaniline

4) 4-amino-N-ethyl-N-(β-hydroxyethyl)aniline

5) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline

6) 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline

7) 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline

8) 4-amino-N-ethyl-N-(β-methanesulfonamide ethyl)-3-methylaniline

9) 4-amino-N, N-diethyl-3-(β-hydroxyethyl)aniline

10) 4-amino-3-methyl-N-ethyl-N-(β-methoxyethyl)aniline

11) 4-amino-3-methyl-N-(β-ethoxyethyl)-N-ethylaniline

14) 4-amino-3-methyl-N-(3-carbamoylpropyl)-N-n-propylaniline

13) 4-amino-3-methyl-N-(4-carbamoylbutyl)-N-n-propylaniline

14) N-(4-amino-3-methylphenyl)-3-hydroxypyrrolidine

15) N-(4-amino-3-methylphenyl)-3-hydroxymethylpyrrolidine

16) N-(4-amino-3-methylphenyl)-3-pyrrolidinecarboxyamide

Among the p-phenylenediamine derivatives indicated in the above,compounds illustrated in 5), 6), 7), 8) and 12) are preferable, andcompounds illustrated in 5) and 8) are particularly preferable. Thesep-phenylenediamine derivatives are, usually in a solid state, a sulfate,a chlorate, a p-toluene sulfonate, a naphthalene disulfonate and a saltof N, N-bis(sulfonic acid ethyl) hydroxylamine. These derivatives may beadded as a free body without a counter salt. A concentration of thearomatic primary amine developing agent in a use solution is in therange from 4 mmol/L to 100 mmol/L, preferably from 6 mmol/L to 50mmol/L, and more preferably from 8 mmol/L to 25 mmol/L.

To the color developing solution of the invention, a compound forpreventing segregation of a color developing agent may be added. Forsuch a compound, polyethylene glycols, aryl sulfonic acids, alkylsulfonic acids or urea compounds described in Japanese Patent Laid-OpenNo. 174643/1999 are mentioned. Among these, diethylene glycol,polyethylene glycol 300, p-toluene sulfonic acid and its salt, an alkylsulfonic acid having a straight chain with 5 to 9 carbon atoms and itssalt and ethylene urea, which show good effects but very littleinfluence to photographic properties, are particularly preferred.

The color development composition of the invention preferably contains acompound for preventing deterioration caused by aerial oxidation of acolor developing agent, namely, a preservative. As inorganicpreservatives, a sulfite and hydroxylamine are preferable. Thesecompounds give a remarkable preservation action. Further, it ispreferable that such an inorganic compound is used with an organicpreservative in combination. In some cases dependent on a photosensitivematerial taken as an object, a sulfite and hydroxylamine may giveunfavorable influences to photographic properties in a color developmentprocess. Therefore, there may be a case that only one of the twocompounds is incorporated, or a case that none of them is substantiallyincorporated but an organic preservative solely used.

Preferable organic preservatives are hydroxylamine derivatives,hydroxamic acids, hydrazides, phenols, monoamines, diamines, polyamines,alcohols, condensed ring-based amines, ring-based amides, salicylicacids, polyethylene imines, alkanol amines, aromatic polyhydroxycompounds, hydroxylamine derivatives described in Japanese PatentLaid-Open No. 56456/1991 and compounds described in Japanese PatentLaid-Open Nos. 33846/1991 and 148841/1994.

In viewpoint of improving stability of the color developing solution ina continuous processing, it is preferred that a hydroxylamine derivativeis used with alkanol amines in combination. As a particularly preferablecompound used with hydroxylamines in combination, tri-isopropanol amineand tri-ethanol amine are mentioned. Further, it is also preferred thata hydroxylamine derivative is used with ring-based amide compounds incombination. Among them, ε-caprolactum is particularly preferred.

A pH value of the color development composition of the invention ispreferably in the range from 9.5 to 13.5. A pH value of the colordeveloping solution prepared from the color development composition ofthe invention is in the range from 9.0 to 12.2, and preferably from 9.9to 11.2. In order to maintain the pH value, a buffer agent is preferablyadded. For a buffer agent, preferred is a potassium salt or a sodiumsalt of an inorganic acid such as a carbonate, a bicarbonate, aphosphate, a borate and a tetraborate. Further, an organic compound suchas 5-sulfosalicylic acid, β-alanine, proline andtris-hydroxyaminomethane is also preferably used. However, the presentinvention should not be construed as being limited thereto. The bufferagent is incorporated in a color development replenisher to become aconcentration of 0.1 mol/L or more, and particularly in the range from0.1 mol/L to 0.4 mol/L.

To the color development composition of the invention, various kinds ofchelating agents, which are precipitation-preventing agents againstmagnesium and the like, can be added. A single kind or two or more kindsof chelating agents may be used. Examples of the preferable chelatingcompound include nitrilo triacetic acid, diethylenetriamine penta-aceticacid, ethylenediamine tetra-acetic acid, N, N, N-trimethylenephosphonicacid, ethylenediamine-N, N, N′, N′-tetramethylenesulfonic acid,ethylenediamine succinic acid (an s, s body),2-phosphonobutane-1,2,4-tricarboxylic acid,1-hydroxyethylidene-1,1-diphosphonic acid and1,2-dihydroxybenzene-4,6-disulfonic acid. The chelating agent may beadded in an amount enough to cover metallic ions in a color developingsolution. An amount of the chelating agent to be added usually in therange from 0.1 g/L to 10 g/L.

To the color development composition of the invention, an optionaldevelopment-accelerator can be added according to necessity. Examples ofthe development-accelerator include polyalkyleneoxide,1-phenyl-3-pyrazolidones, alcohols and carboxylic acids.

To the color development composition of the invention, an optionalanti-foggant can be added according to necessity, As the anti-foggant,metal halides such as sodium chloride, potassium bromide and potassiumiodide and organic anti-foggants typical ones of which arenitrogen-containing heterocyclic compounds are mentioned. Examples ofthe organic anti-foggant include benzotriazole, 6-nitrobenzimidazole,5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,5-chlorobenzotriazole, 2-thiazolylbenzimidazole,2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolidine andadenine. Further, other alkylcarboxylic acids, arylcarboxylic acids andsugars may be added according to necessity.

In case of a color print photosensitive material in the colordevelopment to which the invention is applied, a processing temperatureis in the range from 30° C. to 55° C., preferably from 35° C. to 50° C.,and more preferably from 38° C. to 45° C. A processing time is in therange from 5 seconds to 90 seconds, preferably from 8 seconds to 60seconds, and more preferably from 10 seconds to 45 seconds. Although theless amount of replenishing is the better, an amount of replenishing inthe range from 15 mL to 200 mL per 1 m² of the photosensitive materialis adequate, preferably from 20 mL to 120 mL, and more preferably from30 mL to 60 mL.

In case of a color negative film, a processing temperature is in therange from 30° C. to 55° C., preferably from 35° C. to 50° C., and morepreferably from 38° C. to 45° C. A processing time is in the range from45 seconds to 5 minutes, preferably from 60 seconds to 4 minutes, andmore preferably from 90 seconds to 3 minutes and 15 seconds. Althoughthe less amount of replenishing is the better, an amount of replenishingin the range from 10 mL to 200 mL per 1 roll for 24 exposures isadequate, preferably from 12 mL to 60 mL, and more preferably from 15 mLto 30 mL.

In case of a color reversal film, a processing temperature is in therange from 32° C. to 45° C., preferably from 35° C. to 40° C., and morepreferably from 36.5° C. to 39.5° C. A processing time is in the rangefrom 4 minutes to 8 minutes, preferably from 5 minutes to 7 minutes, andmore preferably from 5 minutes and 30 seconds to 6 minutes and 30seconds. Although the less amount of replenishing is the better, anamount of replenishing in the range from 1000 mL to 3000 mL per 1 m² ofthe photosensitive material is adequate, preferably from 1500 mL to 2800mL, and more preferably from 2000 mL to 2400 mL.

Examples of the preferable mode include color development compositionscondensed from replenishing solutions described in Japanese PatentLaid-Open Nos. 174643/1999, 194461/1999 and 194462/1999.

For a bleaching agent to be used in the bleach composition and the blixcomposition of the invention, known bleaching agents can be used.Particularly preferable are organic complex salts of iron (III) (e.g.,complex salts of organic acids such as aminopolycarboxylic acids orcitric acid, tartaric acid and malic acid), a persultate and hydrogenperoxide. Further, two or more kinds of bleaching agents may be used asa mixture.

Among these, organic complex salts of iron (III) are particularlypreferable in viewpoint of rapid processing and prevention ofenvironmental pollution. Aminopolycarboxylic acids or their salts, whichare useful to form organic complex salts of iron (III), can beenumerated as follows: from biodegradable compounds such asethylenediamine succinic acid (an s, s-body),N-(2-carboxylatethyl)-L-aspartic acid, β-alanine diacetic acid andmethylimino diacetic acid to ethylenediamine tetra (acetic acid),diethylenetriamine penta (acetic acid), 1,3-propylenediamine tetra(acetic acid), nitrilo triacetic acid, cyclohexanediamine tetra-aceticacid and imino diacetic acid. These compounds may be any salt of sodium,potassium, lithium or ammonium. Further, the chelating agent may be usedin excess over the amount needed to form a ferric complex salt. Aconcentration of the bleaching agent in the bleach solution or the blixsolution as a use solution is in the range from 0.01 mol/L to 1.0 mol/L,preferably from 0.05 mol/L to 0.5 mol/L, and more preferably from 0.1mol/L to 0.5 mol/L.

It is also preferable to add the buffer agent into the bleach solutionor the blix solution. The buffer agent is selected in accordance withthe pH value to achieve. Preferable compounds are mentioned as follows:organic acids such as succinic acid, maleic acid, glycolic acid, malonicacid, fumaric acid, sulfosuccinic acid and acetic acid, organic basessuch as imidazole and dimethylimidazole, or compounds represented byFormula (A-a) and Formula (B-b) described in Japanese Patent Laid-OpenNo. 211819/1997. An addition amount of these compounds in a use solutionis preferably in the range from 0.005 mol/L to 3.0 mol/L, and morepreferably from 0.05 mol/L to 1.5 mol/L. A pH range of the bleachsolution is preferably from pH 2 to pH 7, and in particular, preferablyfrom pH 3 to pH 6. In case of the blix solution, the range from pH 3 topH 8 is preferable, and the range from pH 4 to pH 7 is more preferable.

In the blix process of a color print photosensitive material, to whichthe invention is applied, a processing temperature is in the range from30° C. to 55° C., preferably from 35° C. to 50° C., and more preferablyfrom 38° C. to 45° C. A blix time is in the range from 5 seconds to 90seconds, preferably from 8 seconds to 60 seconds, and more preferablyfrom 10 seconds to 45 seconds. Although the less amount of replenishingis the better, an amount of replenishing in the range from 20 mL to 200mL per 1 m² of the photosensitive material is adequate, preferably from25 mL to 120 mL, and more preferably from 30 mL to 50 mL.

In the blix process of a color negative film, a processing temperatureis in the range from 30° C. to 55° C., preferably from 35° C. to 50° C.,and more preferably from 38° C. to 45° C. A blix time is in the rangefrom 12 seconds to 2 minutes, preferably from 15 seconds to 1 minute and15 seconds, and more preferably from 18 seconds to 60 seconds. Althoughthe less amount of replenishing is the better, an amount of replenishingin the range from 2.5 mL to 50 mL per 1 roll for 24 exposures isadequate, preferably from 3 mL to 25 mL, and more preferably from 4 mLto 12 mL.

In the blix process of a color reversal film, a processing temperatureis in the range from 30° C. to 45° C., preferably from 33° C. to 40° C.,and more preferably from 37° C. to 39° C. A blix time is in the rangefrom 4 minutes to 8 minutes, preferably from 5 minutes to 7 minutes, andmore preferably from 5 minutes and 30 seconds to 6 minutes and 30seconds. Although the less amount of replenishing is the better, anamount of replenishing in the range from 160 mL to 400 mL per 1 m² ofthe photosensitive material is adequate, preferably from 180 mL to 300mL, and more preferably from 200 mL to 250 mL.

A fixing agent to be used in the blix composition or in the fixcomposition of the invention is a known fixing agent, namely, awater-soluble silver halide-dissolving agent like a thiosulfate such assodium thiosulfate or ammonium thiosulfate, a thiocyanate such as sodiumthiocyanate or ammonium thiocyanate, ethylene bis glycolic acid,3,6-dithia-1,8-octanediol, thio ether compounds described in JapanesePatent Laid-Open No. 317055/1992, thioureas, or meso-ionic compoundsdescribed in Japanese Patent Laid-Open Nos. 143757/1992 and 230749/1992.These compounds can be used as a single kind or as two or more kinds ofcompounds mixed in combination. A concentration of the fixing agent inthe fix solution or in the blix solution is preferably in the range from0.3 mol/L to 2 mol/L, and more preferably from 0.5 mol/L to 1.5 mol/L.

It is preferred to add a buffer agent to the blix composition or to thefix composition. For a preferable buffer agent, heterocyclic organicbases such as imidazole and dimethylimidazole, aminoalkylene sulfonicacids such as taurine, or dibasic acids such as succinic acid, maleicacid and malonic acid are mentioned. A pH value of the blix compositionor of the fix composition is preferably in the range from 3 to 8, andmore preferably from 4 to 7.

The blix composition and the fix composition of the invention preferablycontain a compound that releases a sulfite ion as a preservative,namely, a sulfite, a bisulfite or a metabisulfite. It is preferred thatthese compounds are added as a potassium salt, a sodium salt or anammonium salt. Further, it is also preferred that an arylsulfinic acidsuch as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid andp-aminobenzenesulfinic acid is contained. These compounds are preferablycontained in the use solution in an amount ranged from 0.02 mol/L to 1.0mol/L. As a preservative in addition to those described in the above,ascorbic acid, carbonyl-bisulfite adduct or a carbonyl compound may beadded.

To the blix composition and the fix composition of the invention, thefollowing compounds may be added for improving image preservation:compounds to form a stable silver ion, namely, mercaptonitrogen-containing heterocyclic compounds such as mercaptotriazole,aminomercaptotriazole and N-methylmercaptoimidazole, or compounds toaccelerate washing-out of a developing agent such as bis amidines andbis guanidines described in Japanese Patent Laid-Open No. 303185/1993 ormonoamidines. In addition to the above, to the blix composition and thefix composition of the invention, polymers such as polyethylene glycoland polyvinylpyrrolidone, chelating agents, anti-foaming agents andfungicides may be added according to necessity.

In the blix process of a color print material, to which the invention isapplied, a processing temperature, a blix time and an amount ofreplenishing are just as described in the above. In the fixing processof a color negative film, a processing temperature is in the range from30° C. to 55° C., preferably from 35° C. to 50° C., and more preferablyfrom 38° C. to 45° C. A bleaching time is in the range from 20 secondsto 2 minutes, preferably from 30 seconds to 1 minute and 40 seconds, andmore preferably from 35 seconds to 1 minute and 20 seconds. Although theless amount of replenishing is the better, an amount of replenishing inthe range from 4 mL to 60 mL per 1 roll foe 24 exposures is adequate,preferably from 5 mL to 40 mL, and more preferably from 6 mL to 30 mL.

In the fixing process of a color reversal film, a processing temperatureis in the range from 30° C. to 45° C., preferably from 33° C. to 40° C.,and more preferably from 37° C. to 39° C. A fixing time is in the rangefrom 2 minutes to 6 minutes, preferably from 3 minutes to 5 minutes, andmore preferably from 3 minutes and 30 seconds to 4 minutes and 30seconds. Although the less amount of replenishing is the better, anamount of replenishing in the range from 800 mL to 2000 mL per 1 m² ofthe photosensitive material is adequate, preferably from 900 mL to 1500mL, and more preferably from 1000 mL to 1250 mL.

To the washing composition and the stabilization composition of theinvention, formalin, acetaldehyde, pyruvinaldehyde,formaldehyde-bisulfite adducts described in U.S. Pat. No. 4,921,778 orN-methylol compounds described in Japanese Patent Laid-Open No.34889/1993 may be added for preventing color-fading of a dye andstain-formation caused by a residual magenta coupler. Further, anarylsulfinic acid such as p-toluenesulfinic acid,m-carboxybenzenesulfinic acid and p-aminobenzenesulfinic acid ispreferably contained. Furthermore, a surfactant as a water-drainingagent, a chelating agent as a hard water-softening agent, a buffer agentfor adjusting a pH value, an anti-foaming agent, a fungicide and agermicide may be added according to necessity.

A pH value of the washing composition or of the stabilizationcomposition is preferably in the range from 4 to 10, and more preferablyfrom 5 to 8. Although a processing temperature can be set in a varietydepending on a usage or on properties of a photosensitive material, itis generally in the range from 20° C. to 50° C., and preferably from 25°C. to 45° C.

A photographic element processed with the processing composition of theinvention can contain a silver halide usually used in a photosensitivematerial, for example, any of silver chloride, silver bromide,silveriodobromide, silver chlorobromide, silver iodochloride and amixture of them. In a mode, this photosensitive element is a silverchloride-rich element containing at least 50 mol % or more of chloride,and more preferably at least 90 mol % or more of chloride. For example,the silver chloride-rich element is often used for a color printphotosensitive material.

In another mode, at least one kind of an emulsion is mainly silverbromide (at least 50 mol % of silver bromide). Most preferably, thisphotographic element has one or more kinds of color recordings, and eachcolor recording has one or more kinds of silver bromide-rich emulsions.The photographic element processed in execution of the invention can bea single color element or a multi-color element. Further, to thephotographic element, a magnetic recording layer known to public in thetechnical field of the industry can be incorporated.

Details of each photographic element are, for example, described inResearch Disclosure (hereinafter abbreviated as RD). RD 17634, pp. 23 to27, RD 18716, pp. 647 to 650, RD 307105, pp. 866 to 868, pp. 873 to 879,and RD 36544, pp. 501 to 541 can be cited. These relate to useful silverhalide emulsions (a negative type or a positive type) and theirpreparation methods, various kinds of sensitizers, dye-forming couplers,image-dye stabilizers, dyes, ultraviolet light-absorbing agents,filters, binders, hardeners, plasticizers, lubricants, coating-aids,surfactants, static charge-preventing agents, matting agents, paper orfilm supports, or various image-forming methods using a color element toform a negative image or a positive image.

In case that the processing compositions of the invention are preparedprocessing agent compositions to be mixed, it is advantageous that thewhole components contained in the use solution are comprised in onecomposition, namely, a one-part-structure. However, when it is notdesirable that components make a contact one another in a long time inthe color development composition or the blix composition, componentsmay be separated into two or more liquid parts or solid parts or both ofthem to make a processing composition having a two-part-structure or athree-part-structure. Such structures of prepared processing agentcompositions to be mixed are usually called as a 1-, 2- or3-part-structure according to the naming by the International StandardsISO 5989. The processing compositions of the invention do not lose theireffects and features of the invention through being separated intoparts. Among them, the 1-part-structure is particularly preferable forthe color development composition.

For a container of the processing composition of the invention, a knownmaterial in accordance with the content can be used. The container maybe made of a single material or a composite material, for example, acomposite material comprising a material of high gas permeability and amaterial of high stability against alkali. In viewpoint of reusabilityand recyclability, it is preferred that the container is structured witha single raw material. Examples of the material to be used for thecontainer include a polyester resin, a polyolefin resin, an acryl resin,an ABS resin, an epoxy resin, a polyamide resin such as Nylon, apolyurethane resin, a polystyrene resin, a polycarbonate resin, PVA,polyvinyl chloride, polyvinylidene chloride and a polyethylene resin.Among them, a container made of a polyester resin such as polyethyleneterephthalate or polyethylene naphthalate or of a polyolefin resin suchas polyethylene or polypropylene as a single material is preferable. Apolyethylene resin is more preferable and a high density typepolyethylene resin (HDPE) is furthermore preferable as a material forthe container.

Into the material for the container to be used in the invention, carbonblack, titanium white, a pigment, calcium carbonate or a plasticizerhaving compatibility with the material can be incorporated, as far as itgives no influence to the processing composition. A material having apolyethylene content ratio of 85% or more and containing no plasticizeris preferred for the material of the container. A material having apolyethylene content ratio of 95% or more and containing no plasticizeris furthermore preferred.

A shape and a structure of the container to be charged with theprocessing composition of the invention can optionally be designedaccording to the purpose. In addition to a standard-shaped bottle,expansion and contraction-flexible type containers described in JapanesePatent Laid-Open No. 235950/1989 and containers with a flexiblepartition described in Japanese Patent Laid-Open No. 134626/1987 canalso be used. Containers described in Japanese Patent Laid-Open No.282148/1999 are particularly preferable for the container of theprocessing composition of the invention from viewpoints of capacity,space efficiency, self-standing ability, shape-keeping capability andreuse or recycle. A preferable mode is a kit in which a plurality of theprocessing compositions of the invention are each charged in containersmade of a single component material and having the same shape andvolume, and further these containers are inserted in a single cartridge.As an example of the cartridge, cartridges described in Japanese PatentLaid-Open No. 3014/2000 can be cited. Cartridges described in JapanesePatent Laid-open Nos. 295858/1999 and 288068/1999 are preferable modesin which a development composition, a bleach composition and a fixcomposition are put in.

Modes and effects of the present invention will be explained in moredetail with EXAMPLES hereinafter. However, the invention is notconstrued as being limited thereto.

EXAMPLE 1

As shown in the following, a prepared processing agent in a condensedliquid form for color development was prepared and its stability wastested.

(1) Preparation of Color Development Composition

A compound represented by Formula (I) of the invention

Refer to TABLE 1

A compound represented by Formula (II) of the invention

Refer to TABLE 1

Tri(isopropanol)amine 40.0 g Ethylenediamine tetra(acetic acid) 15.0 gSodium sulfite 0.80 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 2.0 gDisodium-N,N-bis(sulfonatethyl)hydroxylamine 55.0 g4-amino-3-methyl-N-ethyl-N-(β-methanesulfon- 70.0 g amideethyl)aniline3/2 sulfate monohydrate Potassium hydroxide 34.5 g Sodium hydroxide 25.0g Potassium carbonate 100.0 g Water to make 1000 mL pH 13.2

(2) Evaluation

Stability against deposit segregation of the condensed processingcomposition described in the above was evaluated by a method describedbelow.

The prepared color development composition was charged in a glass bottleand stored during four weeks at −5° C. and at a room temperature. Thetest results were evaluated by visual measurement of the liquidcondition after storage according to five-step-evaluation as follows: alevel with remarkable deposit was expressed as XX; a level with distinctdeposit was expressed as X; a level with slight deposit was expressed asΔ; a level without deposit but with a turbidity was expressed as O; anda clear level without both of deposit and a turbidity pressed as OO.

TABLE 1 Compound Compound Evaluation represented represented Evaluationof by Addition by Addition of Segregation Formula Amount Formula AmountSegregation (room Sample (I) mmol (II) mmol (−5° C.) temp.) Note 1 — — —— XX X Comp 2 — — S-3 35 X X Comp 3 P-1 25 — — Δ Δ Comp 4 P-1 10 S-3 35◯ ◯◯ Inv 5 P-1 25 S-3 35 ◯◯ ◯◯ Inv 6 P-1 25 S-4 35 ◯◯ ◯◯ Inv 7 P-1 25S-6 35 ◯ ◯◯ Inv 8 P-1 25 S-7 35 ◯ ◯◯ Inv 9 P-2 25 S-3 35 ◯◯ ◯◯ Inv 10P-3 25 S-3 35 ◯◯ ◯◯ Inv 11 P-9 25 S-3 35 ◯◯ ◯◯ Inv 12  P-10 25 S-3 35 ◯◯◯ Inv Inv: The Present Invention Comp: Comparative Example

(3) Results

In the composition without both of a compound represented by Formula (I)and a compound represented by Formula (II), occurred needle likecrystals considered as free bases of developing agent. Similar crystalswere observed in the composition using either of compounds.Nevertheless, the compounds using both of a compound represented byFormula (I) and a compound represented by Formula (II) did not form anyneedle-like crystals to show that developing agents were dissolved in astabilized condition.

EXAMPLE 2

By using the composition of Sample 5 in EXAMPLE 1, the followingphotosensitive material sample was continuously processed.

(1) Preparation of Photosensitive Material Sample

After a corona discharge treatment was performed on the surface of asupport comprising both surfaces of paper coated with a polyethyleneresin, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided on the support, and further, layers from thefirst layer to the seventh layer were coated in order, thereby a silverhalide color photographic photosensitive material P-1 having the layerconstitution shown below was prepared. The coating solutions for eachphotographic constitution layer were prepared as follows.

Preparation of Fifth Layer Coating Solutions

300 g of Cyan Coupler (ExC-1), 250 g of Color Image Stabilizer (Cpd-1),10 g of Color Image Stabilizer (Cpd-9), 10 g of Color Image Stabilizer(Cpd-10), Color Image Stabilizer (Cpr-12), 14 g of Ultraviolet LightAbsorber (UV-1), 50 g of Ultraviolet Light Absorber (UV-2), 40 g ofUltraviolet Light Absorber (UV-3) and 60 g of Ultraviolet Light Absorber(UV-4) were dissolved in 230 g of Solvent (Solv-6) and 350 mL of ethylacetate. This solution was emulsion-dispersed into 6500 g of a 10%gelatin aqueous solution containing 25 g of sodiumdodecylbenzenesulfonate, thereby Emulsified Dispersion C was prepared.

On the other hand, Silver Chlorobromide Emulsion C [cubic grains; a 5:5mixture (molar ratio in terms of silver) of Large Grain Emulsion Chaving an average grain size of 0.40 μm and Small Grain Emulsion Chaving an average grain size of 0.30 μm; variation coefficients of grainsize distribution were 0.09 and 0.11 respectively; in both emulsions,silver bromide of 0.5 mol % was localized on apart of grain surfacefundamentally made of silver chloride] was prepared,

In this emulsion, red sensitive Sensitizing Dye G and Sensitizing Dye Hwere respectively added to Large Grain Emulsion C in an amount of9.0×10⁻⁵ mol per 1 mol of silver and to Small Grain Emulsion C in anamount of 12.0×10⁻⁵ mol per 1 mol of silver. Further, chemicalsensitization for this emulsion was optimally performed with addition ofa sulfur sensitizer and a gold sensitizer.

Emulsified Dispersion C and Silver Chlorobromide Emulsion C described inthe above were mixed and dissolved to obtain the composition describedbelow, thereby Fifth Layer Coating Solution was prepared. A coatedamount of emulsion was expressed in a coated amount calculated in termsof silver.

First Layer to Fourth Layer Coating Solutions and Sixth Layer to SeventhLayer Coating Solutions were prepared in the same manner as that inFifth Layer Coating Solution. As a hardener for gelatin in each layer,sodium salt of 1-oxy-3, 5-dichloro-s-triazine was used. Further, to eachlayer, Preservative (Ab-1), (Ab-2), (Ab-3) and (Ab-4) were added so asto obtain an entire amount of 15.0 mg/m², 60.0 mg/m², 5.0 Mg/m² and 10.0mg/m² respectively

Preservative (Ab-1)

Preservative (Ab-2)

Preservative (Ab-3)

Preservative (Ab-4)

R₁ R₂ a —CH₃ —NHCH₃ b —CH₃ —NH₂ c —H —NH₂ d —H —NHCH₃ A mixture of a, b,c and d = 1:1:1:1 (molar ratio)

To the silver chlorobromide emulsion in each photosensitive emulsionlayer, spectral sensitizing dyes indicated below were respectively used.

Blue Sensitive Emulsion Layer

(Sensitizing Dye A and Sensitizing Dye C were added to the large grainemulsion in an amount of 0.42×10⁻⁴ mol per 1 mol of silver halide and tothe small grain emulsion in an amount of 0.50×10⁻⁴ mol. Sensitizing DyeB was added to the large grain emulsion in an amount of 3.4×10⁻⁴ mol per1 mol of silver halide and to the small grain emulsion in an amount of4.1×10⁻⁴ mol.)

Green Sensitive Emulsion Layer

Sensitizing Dye D was added to the large grain emulsion in an amount of3.0×10⁻⁴ mol per 1 mol of silver halide and to the small grain emulsionin an amount of 3.6×10⁻⁴ mol. Sensitizing Dye E was added to the largegrain emulsion in an amount of 4.0×10⁻⁴ mol per 1 mol of silver halideand to the small grain emulsion in an amount of 7.0×10⁻⁴ mol. Further,Sensitizing Dye F was added to the large grain emulsion in an amount of2.0×10⁻⁴ mol per 1 mol of silver halide and to the small grain emulsionin an amount of 2.8×10⁻⁴ mol.)

Red Sensitive Emulsion Layer

Sensitizing Dye C and Sensitizing Dye H were added to the large grainemulsion in an amount of 8.0×10⁻⁵ mol per 1 mol of silver halide and tothe small grain emulsion in an amount of 10.7×10⁻⁵ mol. Further,Compound I indicated below was added to the red sensitive emulsion layerin an amount of 3.0×10⁻³ mol per 1 mol of silver halide.)

To the blue sensitive emulsion layer, the green sensitive emulsion layerand the red sensitive emulsion layer,1-(3methylureidophenyl)-5-mercaptotetrazole was added respectively in anamount of 3.3×10⁻⁴ mol, 1.0×10⁻³ mol and 5.9×10⁻⁴ mol per 1 mol ofsilver halide.

To the second layer, the fourth layer, the sixth layer and the seventhlayer, 1-(3-methylureidophenyl)-5-mercaptotetrazole was addedrespectively in an amount of 0.2 mg/m², 0.2 mg/m², 0.6 mg/m² and 0.1mg/m².

To the blue sensitive emulsion layer and the green sensitive emulsionlayer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added respectivelyin an amount of 1×10⁻⁴ mol and 2×10⁻⁴ mol per 1 mol of silver halide.

To the red sensitive emulsion layer, a latex of a methacrylic acid/butylacrylate copolymer (1:1 by weight ratio; average molecular weight:200,000 to 400,0001 was added in an amount of 0.05 g/m².

To the second layer, the fourth layer and the sixth layer, disodiumcatechol-3,5-disulfonate was added respectively in an amount of 6 mg/m²,6 mg/m² and 18 mg/m².

In order to prevent irradiation, dyes indicated below (a coated amountshown in a parenthesis) were added.

Layer Constitution

The constitution of each layer will be described hereinafter. Numeralsindicate a coated amount (g/m²). In case of a silver halide emulsion,numerals indicate a coated amount calculated in terms of silver.

Support Polyethylene Resin-Laminated Paper

The polyethylene resin on the first layer side contains a white pigment(TiO₂: a content ratio of 16 wt %, ZnO: a content ratio of 4 wt %), afluorescent whitening agent [4, 4′-bis (5-methylbenzoxazolyl) stilbene:a content ratio of 0.03 wt %] and a bluing dye (ultramarine)

First Layer (Blue Sensitive Emulsion Layer): Silver ChlorobromideEmulsion A [cubic grains; a 5:5 0.24 (silver molar ratio) mixture ofLarge Grain Emulsion A having an average grain size of 0.74 μm and SmallGrain Emulsion A having an average grain size of 0.65 μm; variationcoefficients of grain size distribution were 0.08 and 0.10 respectively;both emulsions were incorporated with silver bromide of 0.3 mol %localized on a part of grain surface fundamentally made of silverchloride] Gelatin 1.25 Yellow Coupler (ExY) 0.57 Color Image Stabilizer(Cpd-1) 0.07 Color Image Stabilizer (Cpd-2) 0.04 Color Image Stabilizer(Cpd-3) 0.07 Solvent (Solv-1) 0.21 Second Layer (Color Blend-PreventingLayer): Gelatin 0.99 Color Blend-Preventing Agent (Cpd-4) 0.09 ColorBlend-Preventing Aid (Cpd-5) 0.018 Stabilizer (Cpd-6) 0.13 ColorBlend-Preventing Agent (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent(Solv-2) 0.22 Third Layer (Green Sensitive Emulsion Layer): SilverChlorobromide Emulsion B [cubic grains; a 1:3 0.14 (silver molar ratio)mixture of Large Grain Emulsion B having an average grain size of 0.45μm and Small Grain Emulsion B having an average grain size of 0.35 μm;variation coefficients of grain size distribution were 0.10 and 0.08respectively; both emulsions were incorporated with silver bromide of0.4 mol % localized on a part of grain surface fundamentally made ofsilver chloride] Gelatin 1.36 Magenta Coupler (ExM) 0.15 UltravioletLight Absorber (UV-1) 0.05 Ultraviolet Light Absorber (UV-2) 0.03Ultraviolet Light Absorber (UV-3) 0.02 Ultraviolet Light Absorber (UV-4)0.04 Color Image Stabilizer (Cpd-2) 0.02 Color Blend-Preventing Agent(Cpd-4) 0.002 Stabilizer (Cpd-6) 0.09 Color Image Stabilizer (Cpd-8)0.02 Color Image Stabilizer (Cpd-9) 0.03 Color Image Stabilizer (Cpd-10)0.01 Color Image Stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20 Fourth Layer (ColorBlend-Preventing Layer): Gelatin 0.71 Color Blend-Preventing Agent(Cpd-4) 0.06 Color Blend-Preventing Aid (Cpd-5) 0.013 Stabilizer (Cpd-6)0.10 Color Blend-Preventing Agent (Cpd-7) 0.007 Solvent (Solv-1) 0.04Solvent (Solv-2) 0.16 Fifth Layer (Red Sensitive Emulsion Layer): SilverChlorobromide Emulsion C [cubic grains; a 5:5 0.20 (silver molar ratio)mixture of Large Grain Emulsion C having an average grain size of 0.40μm and Small Grain Emulsion C having an average grain size of 0.30 μm;variation coefficients of grain size distribution were 0.09 and 0.11respectively; both emulsions were incorporated with silver bromide of0.5 mol % localized on a part of grain surface fundamentally made ofsilver chloride] Gelatin 1.11 Cyan Coupler (ExC-1) 0.15 Cyan Coupler(ExC-2) 0.10 Color Image Stabilizer (Cpd-1) 0.25 Color Image Stabilizer(Cpd-14) 0.03 Color Image Stabilizer (Cpd-15) 0.10 Color ImageStabilizer (Cpd-16) 0.08 Color Image Stabilizer (Cpd-17) 0.05 ColorImage Stabilizer (Cpd-18) 0.01 Solvent (Solv-5) 0.23 Sixth Layer(Ultraviolet Light-Absorbing Layer): Gelatin 0.46 Ultraviolet LightAbsorber (UV-1) 0.14 Ultraviolet Light Absorber (UV-2) 0.05 UltravioletLight Absorber (UV-3) 0.04 Ultraviolet Light Absorber (UV-4) 0.06Solvent (Solv-7) 0.25 Seventh Layer (Protective Layer): Gelatin 1.00Acryl-modified copolymer of polyvinyl alcohol (degree 0.04 ofmodification: 17%) Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

(2) Development Processing

The photosensitive material sample described in the above was processedinto a roll-form of 127 mm in width. An experimental processing unit wasused, which was a remodeling of a printer processor for amini-laboratory UCO, Model PP350, manufactured by Fuji Photo Film Co.,Ltd. so as to enable both of a processing time and a processingtemperature to be changed. After being imagewise exposed to lightthrough a negative film of an average density, the photosensitivematerial sample was treated in a continuous processing (a running test)until replenishing had been done in a twice volume as much as a colordevelopment tank in the processing processes described below.

Processing Process Temperature Time Replenishing Volume* ColorDevelopment 45.0° C. 25 sec  45 mL Blix 40.0° C. 25 sec  35 mL Rinse (1)40.0° C.  8 sec — Rinse (2) 40.0° C.  8 sec — Rinse (3)** 40.0° C.  8sec — Rinse (4)** 38.0° C.  8 sec 150 mL Drying   80° C. 15 sec *Areplenishing volume per 1 m² of a photosensitive material **Arinse-cleaning system RC50D manufactured by Fuji Photo Film Co., Ltd.was installed in Rinse (3). A replenishing solution was taken out ofRinse (3) and sent to a reverse osmosis module (RC50D) by means of apump. Permeated water obtained in the tank was supplied to Rinse (4) andcondensed water was returned to Rinse (3). A pump pressure was adjustedto keep a volume of permeated water in the range from 50 mL/min to 300mL/min. Circulation under temperature control was conducted # for 10hours a day. Rinse processes were arranged in a countercurrent systemthrough four tanks from (1) to (4).

The composition of each processing solution is described as follows.

[Solution [Color Developer] in Tank] Water 800 mL P-1 4 mmol S-1 5 mmolTri(isopropanol)amine 8.8 g Ethylenediamine tetra(acetic acid) 4.0 gSodium sulfite 0.10 g Potassium chloride 10.0 g Sodium4,5-dihydroxybenzene-1,3-disulfonate 0.5 gDisodium-N,N-bis(sulfonatethyl)hydroxylamine 8.5 g4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamide 7.0 g ethyl)aniline 3/2sulfuric acid monohydrate Potassium carbonate 26.3 g Water to make 1000mL pH (adjusted by sulfuric acid and potassium 10.35 hydroxide at 25°C.)

For a color development replenishing solution, a solution obtained bydiluting Sample 5 in EXAMPLE 1 with water by 3.8 times was used.

[Blix Solution] [Solution in Tank] [Replenishing solution] Water 800 mL800 mL Ammonium thiosulfate 107 mL 214 mL (750 g/mL) Succinic acid 29.5g 59.0 g Ammonium iron (III) 47.0 g 94.0 g ethylenediamine tetra(acetate) Ethylenediamine tetra 1.4 g 2.8 g (acetic acid) Nitric acid(67%) 17.5 g 35.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0g Ammonium metabisulfite 23.1 g 46.2 g Water to make 1000 mL 1000 mL pH(adjusted by nitric 6.00 6.00 acid and ammonia at 25° C.)

[Replenishing [Rinse Solution] [Solution in Tank] Solution] Sodiumchloroisocyanurate 0.02 g 0.02 g Deionized water (electric 1000 mL 1000mL conductivity: 5 μs/cm or less) pH (25° C.) 6.5 6.5

(3) Results of Evaluation

Stain, gradation and color reproducibility were evaluated asphotographic properties. Each property was good and the conditions ofthe developing solution and of the development replenishing solutionwere normal.

Comparative Examples Comparative Example 1

In COMPARATIVE EXAMPLE 1, conditions and operations were conducted inthe same manner as those in EXAMPLE 2, except that P-1 and S-1 were notadded in the color development solution. An obtained processed sampleshowed dense residual colors to cause stain which produced softgradation in a highlight area and also poor color reproducibilitybecause of brownish overcast of residual colors.

Comparative Example 2

In COMPARATIVE EXAMPLE 2, conditions and operations were conducted inthe same manner as those in EXAMPLE 2, except that P-1 was not added inthe color development solution. An obtained processed sample showedremarkable improvement compared to the sample without both of P-1 andS-1 in Comparative Example 1 described in the above, but still had heavystain to result in clearly worse image quality in comparison with thatof the sample in EXAMPLE 2.

Comparative Example 3

In COMPARATIVE EXAMPLE 3, conditions and operations were conducted inthe same manner as those in EXAMPLE 2, except that S-1 was not added inthe color development solution. An obtained processed sample showedremarkable improvement compared to the sample without both of P-1 andS-1 in Comparative Example 1 described in the above, but still had abrownish white area due to stain caused by residual colors to result inclearly worse image quality in comparison with that of the sample inEXAMPLE 2.

Comparative Example 4

In COMPARATIVE EXAMPLE 4, conditions and operations were conducted inthe same manner as those in EXAMPLE 2, except that P-1 was not added inthe color development solution and the addition amount of S-1 wasdoubled in place of P-1. In spite of the increased amount of S-1, astain level of an obtained processed sample was not equivalent to thelevel of the sample in EXAMPLE 2. Furthermore, the obtained sampleshowed a density decrease in a shadow area to result in worse imagequality with vagueness.

In comparative examples described in the above, the following facts areindicated. When the processing of the invention in which an optimumamount of a compound represented by Formula (I) and an optimum amount ofa compound represented by Formula (II) are respectively selected andused in combination is performed, residual colors of dyes are diminishedfor reducing stain, for producing steeper gradation in a highlight area,and for maintaining a high level of density in a shadow area. On thecontrary, when either one of a compound represented by Formula (I) or acompound represented by Formula (II) is added, even if its additionamount is adjusted, compatibility of stain reduction and gradationkeeping up to a high density level is hardly achieved.

EXAMPLE 3

In this EXAMPLE 3, the photosensitive material and the processing arechanged to show an example in which prepared processing agents are madeand a processing solution is prepared with the prepared processingagents to conduct processing.

(1) Preparation of Color Development Composition

P-1 15 mmol S-1 20 mmol Tri(isopropanol)amine 34.0 g Ethylenediaminetetra(acetic acid) 15.0 g Sodium sulfite 0.80 g Sodium4,5-dihydroxybenzene-1,3-disulfonate 2.0 gDisodium-N,N-bis(sulfonatethyl)hydroxylamine 55.0 g4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamide 55.0 g ethyl)aniline3/2 sulfuric acid monohydrate Potassium hydroxide 19.0 g Sodiumhydroxide 24.0 g Potassium carbonate 100.0 g Water to make 1000 ml pH13.2

(2) Development Processing

The photosensitive material sample described in the above was processedinto a roll-form of 127 mm in width. By using a printer-processor for amini-laboratory use, Model PP350, manufactured by Fuji Photo Film Co.,Ltd., after being imagewise exposed to light through a negative film ofan average density, the photosensitive material sample was treated in acontinuous processing (a running test) until a volume of used colordevelopment replenishing solution had reached a 0.5 times volume as muchas a color development tank in the processing processes described below.

Processing Process Temperature Time Replenishing Volume* ColorDevelopment 38.5° C. 45 sec  45 mL Blix 38.0° C. 45 sec  35 mL Rinse (1)38.0° C. 20 sec — Rinse (2) 38.0° C. 20 sec — Rinse (3)** 38.0° C. 20sec — Rinse (4)** 38.0° C. 20 sec 121 mL Drying   80° C. *A replenishingvolume per 1 m² of a photosensitive material **A rinse-cleaning systemRC50D manufactured by Fuji Photo Film Co., Ltd. was installed in Rinse(3). A replenishing solution was taken out of Rinse (3) and sent to areverse osmosis module (RC50D) by means of a pump. Permeated waterobtained in the tank was supplied to Rinse (4) and condensed water wasreturned to Rinse (3). A pump pressure was adjusted to keep a volume ofpermeated water in the range from 50 mL/min to 300 mL/min. Circulationunder temperature control was conducted # for 10 hours a day. Rinseprocesses were arranged in a countercurrent system through four tanksfrom (1) to (4).

The composition of each processing solution is described as follows.

[Solution [Color Developer] in Tank] Water 800 mL P-1 2 mmol S-3 2 mmolTri(isopropanol)amine 8.8 g Polyethylene glycol (average molecularweight: 300) 10.0 g Ethylenediamine tetra(acetic acid) 4.0 g Sodiumsulfite 0.10 g Potassium chloride 10.0 g Sodium4,5-dihydroxybenzene-1,3-disulfonate 0.50 gDisodium-N,N-bis(sulfonatethyl)hydroxylamine 8.5 g4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamide 4.8 g ethyl)aniline 3/2sulfuric acid monohydrate Potassium carbonate 26.3 g Water to make 1000mL pH (adjusted by sulfuric acid and potassium 10.15 hydroxide at 25°C.)

For a color development replenishing solution, a solution obtained bydiluting the color development composition prepared in (1) by 3.8 timeswith water was used.

[Solution [Replenishing [Blix Solution] in Tank] Solution] Water 800 mL800 mL Ammonium thiosulfate (750 g/mL) 107 mL 214 mLm-carboxybenzenesulfinic acid 8.3 g 16.5 g Ammonium iron (III)ethylenediamine 47.0 g 94.0 g tetra(acetate) Ethylenediaminetetra(acetic acid) 1.4 g 2.8 g Nitric acid (67%) 16.5 g 33.0 g Imidazole14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite23.1 g 46.2 g Water to make 1000 mL 1000 mL pH (adjusted by nitric acidand 6.5 6.5 ammonia water at 25° C.)

[Replen- [Solution ishing [Rinse Solution] in Tank] Solution] Sodiumchloroisocyanurate 0.02 g 0.02 g Deionized water (electric conductivity;5 μs/cm or 1000 mL 1000 mL less) pH (25°0 C.) 6.5 6.5

(3) Results of Evaluation

Stain, gradation and color reproducibility were evaluated asphotographic properties in the same criteria and methods as those inEXAMPLE 2. Each property was good and the conditions of the developingsolution and of the development replenishing solution were normal.

As described in detail in the above, the processing composition of thepresent invention for a silver halide color photographic photosensitivematerial, which contains a bis-triazinylarylenediomine derivativerepresented by Formula (I) and a diaminostilbene derivative representedby Formula (II), shows excellent effects. Namely, stain caused byresidual dyes in the photosensitive material is reduced and nosegregated deposit occurs even when the processing composition is storedat a low temperature. The image-formation process using the processingcomposition of the invention can achieve the same effects.

This application is based on Japanese patent application JP 2000-398271,filed Jul. 24, 2000, and JP 2001-026954, filed Feb. 2, 2001, the entirecontents of each of which are hereby incorporated by reference, the sameas if set forth at length.

What is claimed is:
 1. A processing composition for a silver halidephotographic photosensitive material, which comprises a compoundrepresented by Formula (I) and a compound represented by Formula (II);

wherein x₁, X₂, Y₁ and Y₂ each independently represents a substituted orunsubstituted alkoxy group, a substituted or unsubstituted aryloxygroup, a substituted or unsubstituted anilino group, a substituted orunsubstituted alkylamino group, a substituted or unsubstituteddialkylamino group, a substituted or unsubstituted nitrogen-containingheterocyclic group, a hydroxyl group, a hydroxy organic acid residue, anamino group, an amino acid residue, or a chloro group; and L representsa substituted or unsubstituted phenylene group or a substituted orunsubstituted naphthylene group,

 wherein X₃, X₄, Y₃ and Y₄ each independently represents a substitutedor unsubstituted alkoxy group, a substituted or unsubstituted aryloxygroup, a substituted or unsubstituted anilino group, a substituted orunsubstituted alkylamino group, a substituted or unsubstituteddialkylamino group, a substituted or unsubstituted nitrogen-containingheterocyclic group, a hydroxyl group, a hydroxyl organic acid residue,an amino group, an amino acid residue, and a chloro group; and Mrepresents a hydrogen atom, an alkali metal, an alkali-earth metal,ammonium or pyridinium.
 2. The processing composition for a silverhalide photographic photosensitive material as claimed in claim 1, whichis used in color development processing.
 3. The processing compositionfor a silver halide photographic photosensitive material as claimed inclaim 1, which is used in processing of a silver halide color printphotosensitive material.
 4. An image-formation process using theprocessing composition for a silver halide photographic photosensitivematerial as claimed in claim 1.